Substituted 1-phenyl pyrrolidones and their use as herbicides

ABSTRACT

Substituted 1-phenyl pyrrolidones of the formula   &lt;IMAGE&gt;   in which R1 is halogen, trifluoromethyl, cyano, CH3, CF2CHF2, OCF2CHF2, OCHF2, OCF3, SCH3, S(O)CH3, SO2CH3, methoxyiminomethyl, methoxyimino-1-ethyl, benzoyloxyiminomethyl, benzoyloxyimino-1-ethyl, pyridyloxy, or pyridyloxy substituted with halogen and/or trifluoromethyl; R2 halogen, cyano, carboxy, carbalkoxy or carbalkoxy substituted with halogen, trifluoromethyl or phenyl; R3 is C1-C4 alkyl or C2-C4 alkenyl; X is H or halogen; Y is H or halogen; Z is O or S; and m and n are zero or 1; are useful as herbicidal agents.

BACKGROUND AND SUMMARY OF THE INVENTION

This invention relates to substituted pyrrolidones and to their use inherbicidal formulations. In particular, this invention relates tosubstituted 1-phenyl pyrrolidones of the formula ##STR2## in which: R¹is a member selected from the group consisting of halogen,trifluoromethyl, cyano, CH₃, CF₂ CHF₂, OCF₂ CHF₂, OCHF₂, OCF₃, SCH₃,S(O)CH₃, SO₂ CH₃, methoxyiminomethyl, methoxyimino-1-ethyl,benzoyloxyiminomethyl, benzoyloxyimino-1-ethyl, pyridyloxy, andpyridyloxy substituted with one or more members of the group consistingof halogen and trifluoromethyl;

R² is a member selected from the group consisting of halogen, cyano,carboxy, carbalkoxy containing an alkyl group of 1 to 8 carbon atoms,and carbalkoxy containing an alkyl group of 1 to 8 carbon atomssubstituted with a member selected from the group consisting of halogen,trifluoromethyl and phenyl;

R³ selected from the group consisting of C₁ -C₄ alkyl and C₂ -C₄alkenyl;

X is a member selected from the group consisting of H and halogen;

Y is a member selected from the group consisting of H and halogen;

Z is a member selected from the group consisting of O and S; and

m and n are independently zero or 1.

The compounds of the present invention, as will be seen from thedescription and test data which follows, have utility as bothpre-emergence and post-emergence herbicides, against a wide range ofplant species. The compounds are of particular interest when used inpre-emergence application.

The terms "herbicide" and "herbicidal" are used herein to denote theinhibitive control or modification of undesired plant growth. Inhibitivecontrol and modification include all deviations from natural developmentsuch as, for example, total killing, growth retardation, defoliation,desiccation, regulation, stunting, tillering, stimulation, leaf burn,and dwarfing. The term "herbicidally effective amount" is used to denoteany amount which achieves such control or modification when applied tothe undesired plants themselves or to the area in which these plants aregrowing, The term "plants" is intended to include germinant seeds,emerging seedlings and established vegetation, including both roots andabove-ground portions.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

Within the scope of the above formula, certain embodiments arepreferred, as follows.

R¹ is preferably halogen, trifluoromethyl, cyano or pyridyloxysubstituted with halogen and/or trifluoromethyl. Preferred pyridyloxygroups are pyrid-2-yloxy. In further preferred embodiments, R¹ ischloro, trifluoromethyl, cyano or pyrid-2-yloxy substituted withhalogen, particularly chloro, and/or trifluoromethyl. In the mostpreferred embodiments, R¹ is trifluoromethyl or cyano.

X is preferably H or fluoro, and most preferably H.

The values of m and n are preferably m=1 and n=zero.

R² is preferably halogen, carboxy or carbalkoxy in which the alkyl groupcontains 1 to 4 carbon atoms. In more preferred embodiments, R² ischloro, carboxy and carbethoxy.

R³ is preferably C₁ -C₄ alkyl. Particularly preferred R³ groups areethyl and vinyl, with ethyl being the most preferred.

Y is preferably H or chloro, with H the most preferred.

Z is preferably O.

The term "carboxy" is used herein to designate the --COOH group, and theterm "carbalkoxy" (used interchangeably with "carboalkoxy") is used todesignate an alkyl ester of this group, i.e., --COOR where R is an alkylgroup of the designated number of carbon atoms. The term "carbethoxy" or"carboethoxy" for example designates --COOC₂ H₅. The term "alkyl" andall groups containing alkyl portions are intended to include bothstraight-chain, branched-chain and cyclic groups. Examples are methyl,ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, t-butyl,2-methyl-n-butyl, n-hexyl, cyclohexyl, and cyclopropylmethyl.

It will be noted that the generic formula representing the substituted1-phenyl pyrrolidones of the present invention indicates two chiralcenters, one at the 3-position and the other at the 4-position of thepyrrolidone ring. The specific compounds disclosed herein each representa mixture of enantiomers at both chiral centers, unless otherwiseindicated. Herbicidal activity for the mixture is an indication ofherbicidal activity for each individual enantiomer. In certain cases,however, one enantiomer will have a greater herbicidal activity than theother enantiomer for a given chiral center. For example, for thosecompounds where Y is H. the enantiomers having the greatest activitywill generally be those in which the R² and R³ groups are trans to eachother.

Compounds where R¹ is meta-trifluoromethyl or metacyano, Y is H, R² ishalo (particularly chloro), and R³ is ethyl are of particular interestfor their tolerance to cotton and wheat crops, tho latter particularlyunder growing conditions commonly in use in Europe.

The compounds of this invention are prepared by a step-wise sequence oftransformations that begins with the preparation of N-alkyl anilinesvariously substituted on the aromatic ring. These N-alkyl anilines areprepared either by

(a) the alkylation of an acetanilide with an alkyl halide and strongbase such as sodium hydride, followed by hydrolysis, or

(b) the reaction of an aniline with an aliphatic aldehyde in thepresence of a water scavenger such as titanium tetrachloride, followedby reduction of the product imine with sodium borohydride.

The N-alkylanilines are then treated with ethyl malonyl chloride in anon-polar solvent such as chloroform, methylene chloride, toluene orbenzene in the presence of an organic base such as triethyl amine orpyridine while maintaining the temperature between 5° C. and 20° C. Theresulting ethyl N-aryl-N-alkylmalonate monoamides are then combined in apolar organic solvent, for example acetonitrile, with equivalent amountsof p-toluenesulfonyl azide and an organic base such as triethylamine toform ethyl N-aryl-N-alkyldiazomalonate monoamides. The dropwise additionof these compounds to a refluxing suspension of rhodium (II) acetatedimer in benzene decomposes the diazo group to nitrogen gas and acarbene species which immediately undergoes intramolecular reaction toform a 3-carboethoxy-4-alkylpyrrolidone ring.

Subsequent treatment of these systems with a chlorinating agent such assulfuryl chloride in a non-polar aprotic solvent such as methylenechloride adds a chlorine to the 3-position of the pyrrolidone ring.Hydrolysis of the ester group with either potassium or sodium hydroxidein water/ethanol mixtures followed by acidification with a mineral acidprovides 3-chloro-3-carboxypyrrolidones which, upon heating neat to140°-170° C. liberate carbon dioxide to form the desired product.

The following are examples of compounds which have been synthesized bythe procedures described above. These examples are offered strictly forpurposes of illustration, and are intended neither to limit nor todefine the invention in any manner.

EXAMPLE 1

This example illustrates the preparation of1-(3-trifluoromethylphenyl)-3-chloro-4-ethyl-2-pyrrolidone in which,according to the above formula, m is 1, n is zero, R¹ is CF₃, R² is Cl,R³ is C₂ H₅, X and Y are both H and Z is O. This compound is representedin Table I below as Compound No. 4.

The synthesis began with the preparation ofm-(N-n-butyl)aminobenzotrifluoride, as follows. A two-liter three-neckedround-bottomed flask equipped with a mechanical stirrer, thermometer,and pressure equalizing addition funnel carrying a nitrogen bubbler wascharged with 64.46 g (0.40 mol) of m-aminobenzotrifluoride. 101.19 g(1.00 mol) of triethylamine, and 200 mL of dry ether. The solution wasstirred and cooled to 3° C. by immersing the flask in an external icebath. Freshly distilled butyraldehyde (36.05 g 0.50 mol) in 200 mL ofether was then added all at once. A solution of titanium tetrachloridein 35 mL of dry benzene was then added dropwise at such a rate that thetemperature did not rise above 5° C. When the addition was complete anadditional 10 mL of butyraldehyde were added and the mixture filteredthrough diatomaceous earth to remove the precipitated titanium dioxide.The ether solvent was then removed in vacuo and the resulting yellow oildissolved in 600 mL of absolute ethanol. The solution was stirredmagnetically and 15.13 g (0.40 mol) of sodium borohydride addedbatchwise in portions of approximately 1 g each at such a rate that thefoaming was controlled. One-half hour after the last addition, gaschromatography (GC) analysis showed the reaction to be complete.

After removal of the bulk of the ethanol in vacuo 250 mL of water wasadded to the residue and the pH adjusted to 8 with concentrated HCl. Theoily aqueous mixture was then extracted with three 100-mL portions ofethyl acetate. The extracts were combined, dried (MgSO₄), and thesolvent removed in vacuo to give a light yellow oil that was distilledunder reduced pressure to yield 54.05 g (62%) ofm-(N-n-butyl)aminobenzotrifluoride as a colorless oil; boiling point62.5-63.5° C. at 0.050 mm Hg.

As an alternative route to the same intermediate.N-(3-trifluoromethylphenyl)-N-butyldichloroacetanilide was formed andconverted as follows. A one-liter round-bottomed flask equipped with amechanical stirrer, heating mantle, pressure equalizing addition funnel,and reflux condenser carrying a nitrogen bubbler was charged with 5.23 g(0.22 mol) of sodium hydride and 100 mL of tetrahydrofuran (THF).freshly distilled from sodium/benzophenone. The suspension was stirred,and a solution of 54.41 g (0.20 mol) of3-trifluoromethyl-dichloroacetanilide in 100 mL of THF was addeddropwise with stirring at such a rate that hydrogen evolution wascontrolled. When the addition was complete, 27.4I g (0.20 mol) ofn-butyl bromide were added all at once and the solution was heated toreflux for 48 hours. The solution was then allowed to cool, and 50 mL of3% aqueous HCl cautiously added.

The THF was then removed under reduced pressure and the crudeN-(3-trifluoromethyl)phenyl-N-butyldichloroacetanilide, weighing 58.15 gwas dissolved in 150 mL of absolute ethanol. A solution of 6.8 g ofsodium hydroxide in 10 mL of water was added all at once. The solutionwas stirred at room temperature for 18 hours at which time the ethanolwas removed in vacuo. The resulting semi-solid was partitioned between100 mL of water and 100 mL of ethyl acetate. The layers were separatedand the aqueous phase extracted with two 50-mL portions of ethylacetate. The organic layers were combined, dried (MgSO₄) and the solventremoved under reduced pressure. Vacuum distillation of the residual oilprovided 14.50 g (33%) of m-(N-n-butyl)aminobenzotrifluoride as acolorless oil; boiling point 62.5°-63.5° C. at 0.05 mm Hg.

Conversion to ethyl N-(3-trifluoromethylphenyl)-N-butylmalonatemonoamide then proceeded as follows. To a 300-mL three-neckedround-bottomed flask equipped with a magnetic stirrer, thermometer, andpressure equalizing addition funnel carrying a nitrogen bubbler wasadded 12.92 g (59.5 mmol) of the aminobenzotrifluoride. 100 mL ofmethylene chloride, and 4.82 g (61.0 mmol) of pyridine. The solution wasstirred, cooled to 5° C. with an external ice bath, and 9.18 g (61.0mmol) of ethyl malonylchloride in 25 mL of methylene chloride added atsuch a rate that the temperature did not rise above 10° C. When theaddition was complete the stirring was continued for one-half hour. Thereaction mixture was then washed with two 150-mL portions of 3% aqueousHCl, followed by 100 mL of water, then dried (MgSO₄), and the solventremoved in vacuo to give 18.56 g (94%) of the monoamide as a tan-yellowoil.

This was then converted to ethylN-(3-trifluorometh-ylphenyl)-N-butyldiazomalonate monoamide as follows.A 100-mL three-necked round-bottomed flask equipped with a magneticstirrer, thermometer, and pressure equalizing addition funnel carrying anitrogen bubbler was charged with 10.00 g (30.2 mmol) of the product ofthe last step. 40 mL of acetonitrile, and 3.05 g (30.2 mmol) oftriethylamine. The solution was stirred and a solution of 5.96 g (30.2mmol) of p-toluenesulfonylazide added dropwise over 15 minutes. Duringthis time there was a three-degree exotherm (to 27° C.). The mixture wasthen allowed to stir at room temperature and after 36 hours silica gelthin-layer chromatography (TLC) (1:1 ethyl acetate/hexanes) showed thereaction to be complete. The solvent was then removed in vacuo and theresidual oil dissolved in 50 mL of ether. The solution was sequentiallywashed with 1.81 g of KOH in 20 mL of water, 0.6 g of KOH in 20 mL ofwater, and 20 mL of water, then dried (Na₂ SO₄) and the solvent removedunder reduced pressure to give 9.81 g (91%) of the N-butyldiazomalonatemonoamide as a pale yellow oil.

To convert this to1-(3-trifluoromethylphenyl)-3-carboethoxy-4-ethyl-2-pyrrolidone, a300-mL three-necked round-bottomed flask equipped with a magneticstirrer, heating mantle, thermometer, pressure-equalizing additionfunnel, and reflux condenser carrying a nitrogen bubbler was chargedwith 190 mg of rhodium (II) acetate dimer and 150 mL of benzene. Thesuspension was stirred, heated to reflux, and a solution of 15.18 g(42.5 mmol) of the N-butyldiazomalonate monoamide in 50 mL of benzenewas added dropwise over one hour. When the addition was complete therefluxing was continued for an additional hour, during which time theslow evolution of nitrogen ceased. The suspension was then allowed tocool to room temperature and filtered through diatomaceous earth toremove the rhodium catalyst. Removal of the solvent under reducedpressure provided a red oil that was purified by medium pressure liquidchromatography (MPLC) on silica gel using 30% ethyl acetate/hexanes aseluant. The yield was 6.89 g (49%) of the pyrrolidone ester as a verypale yellow oil.

As the next step in the procedure, this ester was converted to1-(3-trifluoromethylphenyl)-3-chloro-3-carboethoxy-4-ethyl-2-pyrrolidone.To do this, a 300-mL round-bottomed flask equipped with a magneticstirrer and nitrogen bubbler was charged with 6.89 g (20.9 mmol) of theester and 150 mL of methylene chloride. The solution was stirred and1.85 mL (3.10 g. 23.0 mmol) of sulfuryl chloride added all at once bypipette. After 14 hours at room temperature. GC analysis showed thereaction to be complete. The solution was washed with two 40-mL portionsof water and 40 mL of saturated potassium carbonate solution, then dried(Na₂ SO₄), and the solvent removed under reduced pressure to give 6.80 g(89%) of the converted ester as a thick, pale yellow oil.

The converted ester of the preceding paragraph was then furtherconverted to the acid.1-(3-trifluoromethyl-phenyl)-3-chloro-3-carboxy-4-ethyl-2-pyrrolidone,as follows. To a 250-mL boiling flask equipped with a magnetic stirrerwas added 6.08 g (16.7 mmol) of the ester. 100 mL of ethanol, and 0.67 g(16.7 mmol) of NaOH in 5 mL of water. The mixture was stirred at roomtemperature and after two hours, silica gel TLC (1:1 ethylacetate/hexanes) showed the reaction to be complete. The bulk of theethanol was removed in vacuo and the residue taken up in 50 mL of water.The clear solution was washed with two 40-mL portions of ether,acidified with concentrated HCl, and extracted with three 40-mL portionsof methylene chloride. The methylene chloride extracts were combined anddried (MgSO₄), and the solvent removed under reduced pressure to yield4.96 g (88%) of the acid as a very pale yellow foam.

The acid was then converted to the final product.1-(3-trifluoromethylphenyl)-3-chloro-3-carboxy-4-ethyl-2-pyrrolidone asfollows. To a 100-mL boiling flask equipped with a nitrogen bubbler wasadded 4.33 g (12.9 mmol) of the acid. The flask was then heated with aheat gun which converted the foam to a mobile oil. Further heatingeffected the evolution of carbon dioxide as evidenced by vigorous bubbleformation, When the gas evolution had ceased the flask and its contentswere allowed to cool to room temperature affording 3.64 g (97%) ofproduct as a thick oil that slowly solidified upon standing. Analysis bycapillary GC showed this material to be a 54:44 trans/cis mixture ofgeometric isomers. The structure of the product was confirmed as that of1-(3-trifluoromethylphenyl)-3-chloro-3-carboxy-4-ethyl-2-pyrrolidone byinfrared spectroscopy (IR), mass spectrometry (MS) and nuclear magneticresonance (NMR).

EXAMPLE 2

This example illustrates the preparation of1-(3-trifluoromethylphenyl)-3-carbo-t-butoxy-4-ethyl-2-pyrrolidone inwhich, according to the above formula, m is 1 n is zero, R¹ is CF₃, R²is COO-t-C₄ H₉, R³ is C₂ H₅, X and Y are both H, and Z is O. Thiscompound is represented in Table I below as Compound No. 30.

The starting material for this compound was1-(3-trifluoromethylphenyl)-3-carboxy-4-ethyl-2-pyrrolidone, prepared asdescribed in Example 1. where it is an intermediate toward the finalcompound. To convert this ester to the acid the following procedure wasused.

A 500-mL boiling flask equipped with a magnetic stirrer was charged with14.00 g (42.5 mmol) of the ester and 150 mL of ethanol. The solution wasstirred and 2.81 g (42.5 mmol) of 85% KOH in 10 mL of water was addedall at once. The stirring was continued at room temperature overnight atwhich time the bulk of the ethanol was removed under reduced pressure.The residual syrup was dissolved in 250 mL of water and extracted withthree 75-mL portions of methylene chloride. The aqueous layer wasacidified with concentrated HCl and the extraction process repeated. Theacidic extracts were combined and dried (MgSO₄), and the solvent removedunder reduced pressure to provide 12.8 g (100%) of the acid as acolorless foam.

The acid was then converted to the t-butyl ester as follows. A 100-mLthree-necked round-bottomed flask equipped with a magnetic stirrer,thermometer, and pressure equalizing addition funnel carrying a nitrogenbubbler was charged with 2.00 g (6.6 mmol) of carboxylic acid. 25 mL ofbenzene, and four drops of dimethylformamide (DMF). The solution wasstirred and 0.62 mL (0.90 g. 7.1 mmol) of oxalyl chloride added all atonce by pipette. When the evolution of gas had ceased the flask wasimmersed in an external ice bath and the contents cooled to 5° C. Asolution of 0.50 g (6.8 mmol) of t-butanol and 0.56 g (7.1 mmol) ofpyridine in 10 mL of benzene was added dropwise over 10 minutes. Whenthe addition was complete the stirring was continued for 1.5 hours. Atthe end of this time the solution was washed with two 50-mL portions ofwater, then 50 mL of 3% aqueous HCl, then dried (MgSO₄). The solvent wasremoved under reduced pressure to afford 2.34 g (99%) of product as avery pale yellow oil. The structure was confirmed as that of1-(3-trifluoromethylphenyl)-3-carbo-t-butoxy-4-ethyl-2-pyrrolidone byIR, MS and NMR.

These and further compounds prepared by similar procedures are listed inTable I below, together with physical data in the form of refractiveindices or melting points where such measurements were possible, andphysical descriptions where they were not.

                                      TABLE I                                     __________________________________________________________________________    COMPOUNDS                                                                      ##STR3##                                                                     [In this table, Z is 0 except where otherwise indicated.]                                                             n.sub.D.sup.30 or                     No.                                                                              R.sup.1      X Y R.sup.2       R.sup.3                                                                             m.p. °C.                       __________________________________________________________________________    1  CF.sub.3     H H COOC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                     1.5133                                2  CF.sub.3     H Cl                                                                              COOC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                     thick syrup                           3  CF.sub.3     H Cl                                                                              COOH          C.sub.2 H.sub.5                                                                     thick syrup                           4  CF.sub.3     H H Cl            C.sub.2 H.sub.5                                                                     53-59                                 5  CF.sub.3     F H OC.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                     1.5046                                6  CF.sub.3     F Cl                                                                              COOC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                     thick syrup                           7  CF.sub.3     F Cl                                                                              COOH          C.sub.2 H.sub.5                                                                     thick syrup                           8  CF.sub.3     F H Cl            C.sub.2 H.sub.5                                                                     waxy solid                            9  [4-CF.sub.3 -6-Cl-pyrid-2-yloxy]                                                           H H COOC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                     thick syrup                           10 [4-CF.sub.3 -6-Cl-pyrid-2-yloxy]                                                           H Cl                                                                              COOC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                     thick syrup                           11 [4-CF.sub.3 -6-Cl-pyrid-2-yloxy]                                                           H Cl                                                                              COOH          C.sub.2 H.sub.5                                                                     thick syrup                           12 [4-CF.sub.3 -6-Cl-pyrid-2-yloxy]                                                           H H Cl            C.sub.2 H.sub.5                                                                     thick syrup                           13 CF.sub.3     H H COOH          C.sub.2 H.sub.5                                                                     thick syrup                           14 CF.sub.3     H H CN            C.sub.2 H.sub.5                                                                     waxy solid                            15 CF.sub.3     H H COOC.sub.2 H.sub.5                                                                          n-C.sub.3 H.sub.7                                                                   1.5070                                16 CF.sub.3     H H Cl            C.sub.2 H.sub.5                                                                     89-92                                 [Compound No. 16 is the pure trans-isomer of Compound No.                     4, which is a 54:46 trans:cis mixture.]                                       17 CF.sub.3     H H Cl            n-C.sub.3 H.sub.7                                                                   waxy solid                            18 CF.sub.3     H Cl                                                                              COOH          n-C.sub.3 H.sub.7                                                                   thick syrup                           19 CF.sub.3     H Cl                                                                              COOC.sub.2 H.sub.5                                                                          n-C.sub.3 H.sub.7                                                                   thick syrup                           20 Cl           H H COOC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                     1.5538                                21 Cl           H Cl                                                                              COOC.sub.2 H.sub.5                                                                          1.5570                                      22 Cl           H Cl                                                                              COOH          C.sub.2 H.sub.5                                                                     thick syrup                           23 Cl           H H Cl            C.sub.2 H.sub.5                                                                     waxy solid                            24 CF.sub.3     H Cl                                                                              Cl            C.sub.2 H.sub.5                                                                     waxy solid                            25 H            H H Cl            C.sub.2 H.sub.5                                                                       89-93.5                             26 CN           H H Cl            C.sub.2 H.sub.5                                                                     74-85                                 27 CF.sub.3     H H COOC.sub.2 H.sub.5                                                                          CHCH.sub.2                                                                          1.5126                                28 CF.sub.3     H H COOC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                     thick syrup                           [In Compound No. 28, Z = S]                                                   29 CF.sub.3     H H COOCH(CH.sub.3)C.sub.6 H.sub.5                                                              C.sub.2 H.sub.5                                                                     1.5220                                30 CF.sub.3     H H COO-t-C.sub.4 H.sub.9                                                                       C.sub.2 H.sub.5                                                                     1.4829                                31 CF.sub.3     H H COOC(CH.sub.3).sub.2C.sub.2 H.sub.5                                                         C.sub.2 H.sub.5                                                                     1.4829                                32 CF.sub.3     H H COO(CH.sub.2).sub.2C(CH.sub.3).sub.3                                                        C.sub.2 H.sub.5                                                                     waxy solid                            33 CF.sub.3     H H COOCH(CH.sub.3)C.sub.3 H.sub.5                                                              C.sub.2 H.sub.5                                                                     1.4811                                34 CF.sub.3     H H COOCH.sub.2C(C.sub.2 H.sub.4 *)CH.sub.3                                                     C.sub.2 H.sub.5                                                                     56-65                                 35 CF.sub.3     H H COO-t-C.sub.4 H.sub.9                                                                       C.sub.2 H.sub.5                                                                     waxy solid                            36 CF.sub.3     H H COOC(CH.sub.3).sub.2CHCl                                                                    C.sub.2 H.sub.5                                                                     thick syrup                           37 CF.sub.3     H H COOC(CH.sub.3).sub.2CF.sub.3                                                                C.sub.2 H.sub.5                                                                     1.4641                                __________________________________________________________________________     [* in Compound Nos. 33 and 34 denotes cyclopropyl ring.]-                

The compounds listed in the foregoing table were tested for herbicidalactivity by various methods and at various rates of application. Theresults of some of these tests are given below. As one skilled in theart is aware, the results obtained in herbicidal screening tests areaffected by a number of factors that are not readily controllable.Environmental conditions such as amount of sunlight and water, soiltype, soil pH, temperature and humidity, are examples of such factors.The depth of planting and the application rate of the herbicide, as wellas the nature of crops being tested, can also affect the test results.Results will also vary from crop to crop and within the crop varieties.

The test procedures used are as follows:

Pre-Emergence Herbicidal Evaluation at 4 lb/acre

Planting flats were filled with sandy loam soil containing a fungicideand fertilizer. The soil was leveled and rows of grassy weeds, broadleafweeds and yellow nutsedge (Cyperus esculentus), were planted thicklyenough so that several seedlings emerged per inch of row. The grassyweeds were yellow foxtail (Setaria viridis), watergrass (Echinochloacrusgalli) and wild oat (Avena fatua). Broadleaf weeds utilized wereannual morningglory (Ipomoea purpurea). velvetleaf (Abutilontheophrasti), wild mustard (Brassica kaber), and curly dock (Rumexcrispus).

Solutions of the test compounds were made by weighing out 333 mg of thetest compound into a 60-mL wide-mouth bottle, then dissolving thecompound in 25 mL of acetone containing 1% Tweene® 20 (polyoxyethylenesorbitan monolaurate emulsifier). Additional solvents, not exceeding 5mL, were used if needed to dissolve the compound. A 20.5-mL aliquot wasthen taken from the solution and diluted with 25 mL of an acetone:watermixture (19:1) containing 1% Tweene® 20. This was used as the spraysolution.

One day after planting, the flats were sprayed with the spray solutionat a rate of 80 gallons of solution per acre with the compound beingapplied at a rate of 4 pounds per acre (4.48 kg/hectare).

The flats were then returned to the greenhouse and watered daily bysprinkling. The degree of weed control was estimated and recorded 3weeks after treatment, as percentage control compared to the growth ofthe same species in an untreated check flat of the same age.

The percent control is the total injury to the plants due to allfactors, including inhibited germination, killing of the plant tissueafter emergence, stunting, malformation, chlorosis, and other types ofinjury. The control ratings vary from 0 to 100 percent, where 0represents no effect with growth equal to the untreated control, and 100represents complete kill; a dash indicates that no test was performed atthat level of application.

Post-Emergence Herbicidal Evaluation at 4 lb/acre

The soil was prepared and seeded with the same varieties used in thepre-emergence test. The flats were placed in the greenhouse at 70°-85°F. (21°-29° C.) and watered by sprinkling. Twelve to fourteen days afterplanting, the flats were sprayed at a rate of 80 gallons of solution peracre. Each compound was applied at the rate of 4 pounds/acre (4.48kg/hectare). using a spray solution prepared as in the pre-emergencetest.

The flats were returned to the greenhouse after spraying and watereddaily without wetting the foliage. Three weeks after treatment thedegree of weed control was estimated and recorded as percentage controlcompared to the growth of the same species in an untreated check flat ofthe same age. The percent control ratings were assigned on the samebasis as for the pre-emergence evaluation.

The following table lists the results of these tests, in terms ofaverages for the grasses and broadleaf weeds, with yellow nutsedgelisted separately, in both pre- and post-emergence evaluations.

                  TABLE II                                                        ______________________________________                                        HERBICIDE TEST RESULTS -                                                      PERCENT CONTROL AT 4 LB/ACRE                                                  Compound Pre-Emergence   Post-Emergence                                       No.      YNS     AVG     AVB   YNS   AVG   AVB                                ______________________________________                                         1       0       63      25    0     37    38                                  2       0       65      20    0     28    34                                  3       0       65      53    0     37    46                                  4       --      --      --    --    --    --                                  5       0       62      31    --    23    51                                  6       0       40      21    --    27    66                                  7       0       60      58    0     35    84                                  8       --      --      --    --    --    --                                  9       0       50      59    0      0    59                                 10       0       17      28    0      0    51                                 11       0       30      28    0     13    61                                 12       30      70      65    0     37    48                                 13       0       17       9    0      0    29                                 14       0       43      36    0     28    40                                 15       0       45      12    0     15    30                                 16       90      97      100   75    68    60                                 17       0       80      73    0     50    63                                 18       0        0       O    0      0    57                                 19       0        0       0    0      0    42                                 20       0       13      17    0      2    25                                 21       0       47       5    0      0    35                                 22       0       20      38    0      2    37                                 23       --      --      --    --    --    --                                 24       --      --      --    --    --    --                                 25       70      95      97    50    67    53                                 26       80      97      99    80    88    80                                 27       0       35      40    0     27    37                                 28       0       53      47    0     40    60                                 29       0       33      33    0     40    50                                 30       0       97      80    0     78    83                                 31       0       53      47    0      0    57                                 32       0       33      23    0      0    70                                 33       0       63      73    0     40    87                                 34       0       57      50    0      7    37                                 35       0       67      40    0     30    87                                 36       0       60      40    0     33    63                                 37       0       63      53    0     40    53                                 ______________________________________                                         Abbreviations:                                                                YNS: Yellow Nutsedge                                                          AVG: Grasses averaged                                                         AVB: Broadleaf weeds averaged                                            

Herbicidal and Crop Injury Tests at 0.25-2.0 lb/acre

Pre-emergence and post-emergence tests were performed at applicationrates ranging from 0.10 to 2.00 lb/acre based on the active ingredient(0.112 to 2.24 kg/hectare) for a number of the compounds listed in TableI. This round of testing extended to both weed and crop species, andfollowed the same general procedure as the 4 lb/acre tests, except forthe plant species used. The species were as follows:

    ______________________________________                                        Grass weeds:                                                                             yellow foxtail                                                                             Setaria viridis                                                  annual ryegrass                                                                            Lolium multiflorum                                               watergrass   Echinochloa crusgalli                                            shattercane  Sorghum bicolor                                                  wild oat     Avena fatua                                                      broadleaf    Brachiaria platyphylla                                           signalgrass                                                                   downy brome  Bromus tectorum                                       Broadleaf weeds:                                                                         annual morning-                                                                            Ipomoea purpurea                                                 glory                                                                         cocklebur    Xanthium pensylvanicum                                           sesbania     Sesbania exasperata                                              velvetleaf   Abutilon theophrasti                                             sicklepod    Cassia obtusifolia                                               wild mustard Brassica kaber                                        Other:     yellow nutsedge                                                                            Cyperus esculentus                                    Crops:     cotton       Gossypium herbaceum                                              soybean      Glycine max                                                      corn         Zea mays                                                         milo         Sorghum vulgare                                                  wheat        Triticum aestivum                                                rice         Oryza sativa                                                     sugarbeet    Beta vulgaris                                         ______________________________________                                    

The results of these test are listed in Table III, in which the indiciaused are the same as those in Table II.

                                      TABLE III                                   __________________________________________________________________________    HERBICIDE AND CROP INJURY TEST RESULTS                                        PERCENT CONTROL AT 2 LB/ACRE AND LESS                                         Crops*                   Weeds                                                Rate                                                                             (1)                                                                              (2)                                                                              (3)                                                                              (4) (5)                                                                              (6)                                                                              (7)                                                                              YNS AVG AVB                                          __________________________________________________________________________    Compound No. 4 - Pre-Emergence:                                               1.00                                                                             90 85 100                                                                              70  100                                                                              90 45 40  100 100                                          0.50                                                                             90 85 100                                                                              70  100                                                                              90 50 40  100 100                                          0.25                                                                             70 60 100                                                                              30  100                                                                              80 20 25  99  90                                           Compound No. 4 - Post-Emergence:                                              1.00                                                                             100                                                                              25 80 45  40 55 60 55  51  85                                           0.50                                                                             100                                                                              40 70 55  30 60 40 65  51  80                                           0.25                                                                             100                                                                              10 25 15  40 20 30 30  39  65                                           Compound No. 8 - Pre-Emergence:                                               1.00                                                                             95 99 98 100 100                                                                              65 100                                                                              75  98  99                                           0.50                                                                             95 65 90 75  100                                                                              40 10 60  95  78                                           0.25                                                                             80 30 90 40  100                                                                              10 10 0   81  72                                           0.10                                                                             60 10 65 10  100                                                                              15 0  0   70  54                                           Compound No. 23 - Pre-Emergence:                                              1.00                                                                             70 25 50 40  100                                                                              45 100                                                                              --  77  42                                           0.50                                                                             35 0  50 40  90 40 30 --  62  38                                           0.25                                                                             10 0  20 30  50 20 25 0   47  15                                           0.13                                                                             0  0  0  30  40 25 100                                                                              0   21  6                                            Compound No. 23 - Post-Emergence:                                             2.00                                                                             90 35 35 40  90 25 0  0   71  72                                           1.00                                                                             40 0  25 15  0  0  35 0   33  39                                           Compound No. 24 - Pre-Emergence:                                              1.00                                                                             75 100                                                                              25 30  100                                                                              45 15 20  89  95                                           0.50                                                                             30 95 10 10  100                                                                              30 0  0   81  62                                           0.25                                                                             20 75 0  0   100                                                                              0  0  0   68  61                                           0.13                                                                             30 10 0  0   100                                                                              30 0  0   62  36                                           Compound No. 24 - Post-Emergence:                                             1.00                                                                             50 25 40 0   100                                                                              35 30 10  78  99                                           0.50                                                                             95 0  15 0   100                                                                              0  10 0   44  61                                           __________________________________________________________________________     *Crops: Crops:                                                                (1) Soybean                                                                   (2) Wheat                                                                     (3) Milo                                                                      (4) Rice                                                                      (5) Sugarbeet                                                                 (6) Corn                                                                      (7) Cotton                                                               

The compounds of the present invention are useful as herbicides and canbe applied in a variety of ways known to those skilled in the art, atvarious concentrations. In practice, the compounds are applied asformulations containing the various adjuvants and carriers known to orused in the industry for facilitating dispersion. The choice offormulation and mode of application for any given compound may affectits activity, and selection will be made accordingly. The compounds ofthe invention may thus be formulated as granules, as wettable powders,as emulsifiable concentrates, as powders or dusts, as flowables, assolutions, suspensions or emulsions, or in controlled-release forms suchas microcapsules. These formulations may contain as little as about 0.5%to as much as about 95% or more by weight of active ingredient. Theoptimum amount for any given compound will depend upon the nature of theseeds or plants to be controlled. The rate of application will generallyvary from about 0.01 to about 10 pounds per acre, preferably from about0.02 to about 4 pounds per acre.

Wettable powders are finely divided particles which disperse readily inwater or other liquid carriers. The particles contain the activeingredient retained in a solid matrix. Typical solid matrices includefuller's earth, kaolin clays, silicas and other readily wet organic orinorganic solids. Wettable powders normally contain about 5% to about95% of the active ingredient plus a small amount of wetting, dispersing,or emulsifying agent.

Emulsifiable concentrates are homogeneous liquid compositionsdispersible in water or other liquid, and may consist entirely of theactive compound with a liquid or solid emulsifying agent, or may alsocontain a liquid carrier, such as xylene, heavy aromatic naphthas,isophorone and other non-volatile organic solvents. In use, theseconcentrates are dispersed in water or other liquid and normally appliedas a spray to the area to be treated. The amount of active ingredientmay range from about 0.5% to about 95% of the concentrate.

Granular formulations include both extrudates and relatively coarseparticles, and are usually applied without dilution to the area in whichsuppression of vegetation is desired. Typical carriers for granularformulations include sand fuller's earth, attapulgite clay, bentoniteclays, montmorillonite clay, vermiculite, perlite and other organic orinorganic materials which absorb or which can be coated with the activecompound. Granular formulations normally contain about 5% to about 25%active ingredients which may include surface-active agents such as heavyaromatic naphthas, kerosene or other petroleum fractions, or vegetableoils; and/or stickers such as dextrins, glue or synthetic resins.

Dusts are free-flowing admixtures of the active ingredient with finelydivided solids such as talc, clays, flours and other organic andinorganic solids which act as dispersants and carriers.

Microcapsules are typically droplets or granules of the active materialenclosed in an inert porous shell which allows escape of the enclosedmaterial to the surroundings at controlled rates. Encapsulated dropletsare typically about 1 to 50 microns in diameter. The enclosed liquidtypically constitutes about 50 to 95% of the weight of the capsule, andmay include solvent in addition to the active compound. Encapsulatedgranules are generally porous granules with porous membranes sealing thegranule pore openings retaining the active species in liquid form insidethe granule pores. Granules typically range from 1 millimeter to 1centimeter, preferably 1 to 2 millimeters in diameter. Granules areformed by extrusion, agglomeration or prilling, or are naturallyoccurring. Examples of such materials are vermiculite, sintered clay,kaolin, attapulgite clay, sawdust and granular carbon. Shell or membranematerials include natural and synthetic rubbers, cellulosic materials,styrene-butadiene copolymers, polyacrylonitriles, polyacrylates,polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other useful formulations for herbicidal applications include simplesolutions of the active ingredient in a solvent in which it iscompletely soluble at the desired concentration, such as acetone,alkylated napthalenes, xylene and other organic solvents. Pressurizedsprays, wherein the active ingredient is dispersed in finely-dividedform as a result of vaporization of a low boiling dispersant solventcarrier, such as the Freons, may also be used.

Many of these formulations include wetting, dispersing or emulsifyingagents. Examples are alkyl and alkylaryl sulfonates and sulfates andtheir salts; polyhydric alcohols; polyethoxylated alcohols; esters andfatty amines. These agents when used normally comprise from 0.1% to 15%by weight of the formulation.

The compounds of the present invention are also useful when combinedwith other herbicides and/or defoliants, dessicants, growth inhibitors,and the like. These other materials can comprise from about 5% to about95% of the active ingredients in the formulations. These combinationsfrequently provide a higher level of effectiveness in controlling weedsand often provide results unattainable with separate formulations of theindividual herbicides.

Examples of other herbicides, defoliants, dessicants and plant growthinhibitors with which the compounds of this invention can be combinedare:

chlorophenoxy herbicides such as 2,4-D, 2,4,5-T, MCPA, MCPB, 2,4-DB,2,4-DEB, 4-CPA, 2,4,5-TB, and silvex;

carbamate herbicides such as propham, chlorpropham, swep, and barban;

thiocarbamate and dithiocarbamate herbicides such as CDEC,metham-sodium, EPTC, diallate, PEBC, and vernolate;

substituted urea herbicides such as norea, dichloral urea, chloroxuron,cycluron, fenuron, monuron, monuron TCA, diuron, linuron, monolinuronneburon, buturon and trimeturon;

symmetrical triazine herbicides such as simazine, chlorazine,desmetryne, norazine, ipazine, prometryn, atrazine, trietazine,simetone, prometone, propazine and ametryne;

chlorinated aliphatic acid herbicides such as TCA and dalapon;

chlorinated benzoic acid and phenylacetic acid herbicides such as2,3,6-TBA, dicamba, tricamba, chloramben, fenac, PBA,2-methoxy-3,6-dichlorophenylacetic acid,3-methoxy-2,6-dichlorophenylacetic acid,2-methoxy-3,5,6-trichlorphenylacetic acid and2,4-dichloro-3-nitrobenzoic acid;

and such compounds as aminotriazole, maleic hydrazide, phenylmercuryacetate, endothal, technical chlordane, DCPA, diquat, erbon, DNC, DNBP,dichlobenil, DPA, diphenamide, dipropalin, trifluralin, solan, dicryl,merphos, DMPA, DSMA, MSMA, potassium azide, acrolein, benefin,bensulide, AMS, bromacil,2-(3,4-dichloro-phenyl)-4-methyl-1,2,4-oxazolidine-3,5-dione,bromoxynil, cacodylic acid, CMA, CPMF, cypromid, DCB, DCPA, dichlone,diphenatril, DMTT, DNAP, EBEP, EXD, HCA, ioxynil, IPX, isocil, potassiumcyanate, MAA, MAMA, MCPES, MCPP, MH, molinate, NPA, OCH, paraquat, PCP,picloram, DPA, PCA, sesone, terbacil, terbutol, TCBA, alachlor,nitralin, sodium tetraborate, calcium cyanamide,S,S,S-tributylphosphorotrithioate and propanil.

These formulations can be applied to the areas where control is desiredby conventional methods. Dust and liquid compositions, for example, canbe applied by the use of power-dusters, boom and hand sprayers and spraydusters, The formulations can also be applied from airplanes as a dustor a spray or by rope wick applications. To modify or control growth ofgerminating seeds or emerging seedlings, dust and liquid formulationscan be distributed in the soil to a depth of at least one-half inchbelow the soil surface or applied to the soil surface only, by sprayingor sprinkling. The formulations can also be applied by addition toirrigation water. This permits penetration of the formulations into thesoil together with the irrigation water. Dust compositions, granularcompositions or liquid formulations applied to the surface of the soilcan be distributed below the surface of the soil by conventional meanssuch as discing, dragging or mixing operations,

The following are examples of typical formulations,

    ______________________________________                                        5% dust:    5     parts active compound                                                   95    parts talc                                                  2% dust:    2     parts active compound                                                   1     part highly dispersed silicic acid                                      97    parts talc                                                  ______________________________________                                    

These dusts are formed by mixing the components then grinding themixture to the desired particle size,

    ______________________________________                                        5% granules:                                                                  5         parts active compound                                               0.25      part epichlorohydrin                                                0.25      part cetyl polyglycol ether                                         3.5       parts polyethylene glycol                                           91        parts kaolin (particle size 0.3-0.8 mm)                             ______________________________________                                    

Granules are formed by mixing the active compound with epichlorohydrinand dissolving the mixture in 6 parts of acetone. The polyethyleneglycol and cetyl polyglycol ether are then added. The resultant solutionis sprayed on the kaolin and the acetone evaporated in vacuo.

    ______________________________________                                        wettable powders                                                              ______________________________________                                        70%:   70     parts active compound                                                  5      parts sodium dibutylnaphthylsulfonate                                  3      parts naphthalenesulfonic acid/phenolsulfonic                                 acid/formaldehyde condensate (3:2:1)                                   10     parts kaolin                                                           12     parts Champagne chalk                                           40%:   40     parts active compound                                                  5      parts sodium lignin sulfonate                                          1      part sodium dibutylnaphthalenesulfonic acid                            54     parts silicic acid                                              25%:   25     parts active compound                                                  4.5    parts calcium lignin sulfate                                           1.9    parts Champagne chalk/hydroxyethyl                                            cellulose (1:1)                                                        1.5    parts sodium dibutylnaphthalenesulfonate                               19.5   parts silicic acid                                                     19.5   parts Champagne chalk                                                  28.1   parts kaolin                                                    25%:   25     parts active compound                                                  2.5    parts isooctylphenoxy-polyethylene-ethanol                             1.7    parts Champagne chalk/hydroxyethyl                                            cellulose (1:1)                                                        8.3    parts sodium aluminum silicate                                         16.5   parts kieselguhr                                                       46     parts kaolin                                                    10%:   10     parts active compound                                                  3      parts of a mixture of sodium salts of                                         saturated fatty alcohol sulfates                                       5      parts naphthalenesulfonic acid/formaldehyde                                   condensate                                                             82     parts kaolin                                                    ______________________________________                                    

These wettable powders are prepared by intimately mixing the activecompounds with the additive in suitable mixers, and grinding theresulting mixtures in mills or rollers.

    ______________________________________                                        25% emulsifiable concentrate:                                                 ______________________________________                                        25      parts active substance                                                2.5     parts epoxidized vegetable oil                                        10      parts of an alkylarylsulfonate/fatty alcohol                                  polyglycol ether mixture                                              5       parts dimethylformamide                                               57.5    parts xylene                                                          ______________________________________                                    

What is claimed is:
 1. A compound having the formula ##STR4## in which:R¹ is a member selected from the group consisting of halogen,trifluoromethyl, cyano, CH₃, CF₂ CHF₂, OCF₂ CHF₂, OCHF₂, OCF₃, SCH₃,S(O)CH₃, SO₂ CH₃, methoxyiminomethyl, methoxyimino-1-ethyl,benzoyloxyiminomethyl, benzoyloxyimino-1-ethyl, pyridyloxy, andpyridyloxy substituted with one or more members of the group consistingof halogen and trifluoromethyl;R² is a member selected from the groupconsisting of halogen, cyano, carboxy, carbalkoxy containing an alkylgroup of 1 to 8 carbon atoms, and carbalkoxy containing an alkyl groupof 1 to 8 carbon atoms substituted with a member selected from the groupconsisting of halogen, trifluoromethyl and phenyl; R³ is a memberselected from the group consisting of C₁ -C₄ alkyl and C₂ -C₄ alkenyl; Xis a member selected from the group consisting of H and halogen; Y is amember selected from the group consisting of H and halogen; Z is amember selected from the group consisting of O and S; and m and n areindependently zero or
 1. 2. A compound according to claim 1 in which mis 1 and n is zero.
 3. A compound according to claim 1 in which m is 1and n is zero, and R¹ is a member selected from the group consisting ofhalogen, trifluoromethyl, cyano, and pyridyloxy substituted with one ormore members of the group consisting of halogen and trifluoromethyl. 4.A compound according to claim 1 in which m is 1 and n is zero, and R¹ isa member selected from the group consisting of chloro, trifluoromethyl,cyano, and pyrid-2-yloxy substituted with one or more members of thegroup consisting of halogen and trifluoromethyl.
 5. A compound accordingto claim 1 in which m is 1 and n is zero. R¹ is trifluoromethyl, and Xis a member selected from the group consisting of H and fluoro.
 6. Acompound according to claim 1 in which m is 1 and n is zero, R¹ istrifluoromethyl, and X is a member selected from the group consisting ofH and fluoro.
 7. A compound according to claim 1 in which R² is a memberselected from the group consisting of halogen, carboxy, and carbalkoxycontaining an alkyl group of from 1 to 4 carbon atoms.
 8. A compoundaccording to claim 1 in which R² is a member selected from the groupconsisting of chloro, carboxy and carbethoxy.
 9. A compound according toclaim 1 in which R² is chloro.
 10. A compound according to claim 1 inwhich R³ is a member selected from the group consisting of ethyl andvinyl.
 11. A compound according to claim 1 in which R³ is C¹ -C⁴ alkyl.12. A compound according to claim 1 in which R³ is ethyl.
 13. A compoundaccording to claim 1 in which Y is a member selected from the groupconsisting of H and chloro.
 14. A compound according to claim 1 in whichY is H.
 15. A compound according to claim 1 in which Z is O.
 16. Acompound according to claim 1 in which m is 1, n is zero, R¹ istrifluoromethyl, R² is chloro, R³ is ethyl, X is H, Y is H, and Z is O.17. A compound according to claim 1 in which m is 1, n is zero, R¹ istrifluoromethyl, R² is chloro, R³ is ethyl, X is fluoro, Y is H, and Zis O.
 18. A compound according to claim 1 in which m is
 1. n is zero, R¹is trifluoromethyl, R² is chloro, R³ is ethyl, X is H, Y is H, and Z isO.
 19. An herbicidal composition comprising:(a) an herbicidallyeffective amount of a compound having the formula ##STR5## in which: R¹is a member selected from the group consisting of halogen,trifluoromethyl, cyano, CH₃, CF₂ CHF₂, OCF₂ CHF₂, OCHF₂, OCF₃, SCH₃,S(O)CH₃, SO₂ CH₃, methoxyiminomethyl, methoxyimino-1-ethyl,benzoyloxyiminomethyl, benzoyloxyimino-1-ethyl, pyridyloxy, andpyridyloxy substituted with one or more members of the group consistingof halogen and trifluoromethyl; R² is a member selected from the groupconsisting of halogen, cyano, carboxy, carbalkoxy containing an alkylgroup of 1 to 8 carbon atoms, and carbalkoxy containing an alkyl groupof 1 to 8 carbon atoms substituted with a member selected from the groupconsisting of halogen, trifluoromethyl and phenyl; R³ is a memberselected from the group consisting of C₁ -C₄ alkyl and C₂ -C₄ alkenyl; Xis a member selected from the group consisting of H and halogen; Y is amember selected from the group consisting of H and halogen; Z is amember selected from the group consisting of O and S; and m and n areindependently zero or 1; and (b) an herbicidally suitable inert diluentor carrier.
 20. An herbicidal composition according to claim 19 in whichm is 1 and n is zero.
 21. An herbicidal composition according to claim19 in which m is 1 and n is zero, and R¹ is a member selected from thegroup consisting of halogen, trifluoromethyl, cyano, and pyridyloxysubstituted with one or more members of the group consisting of halogenand trifluoromethyl.
 22. An herbicidal composition according to claim 19in which m is 1 and n is zero, and R¹ is a member selected from thegroup consisting of chloro, trifluoromethyl, cyano, and pyrid-2-yloxysubstituted with one or more members of the group consisting of halogenand trifluoromethyl.
 23. An herbicidal composition according to claim 19in Which m is 1 and n is zero. R¹ is trifluoromethyl, and X is a memberselected from the group consisting of H and fluoro.
 24. An herbicidalcomposition according to claim 19 in which m is 1 and n is zero, R¹ istrifluoromethyl, and X is a member selected from the group consisting ofH and fluoro.
 25. An herbicidal composition according to claim 19 inwhich R² is a member selected from the group consisting of halogen,carboxy, and carbalkoxy containing an alkyl group of from 1 to 4 carbonatoms.
 26. An herbicidal composition according to claim 19 in which R²is a member selected from the group consisting of chloro, carboxy andcarbethoxy.
 27. An herbicidal composition according to claim 19 in whichR² is chloro.
 28. An herbicidal composition according to claim 19 inwhich R³ is a member selected from the group consisting of ethyl andVinyl.
 29. An herbicidal composition according to claim 19 in which R³is C¹ -C⁴ alkyl.
 30. An herbicidal composition according to claim 19 inwhich R³ is ethyl.
 31. An herbicidal composition according to claim 19in which Y is a member selected from the group consisting of H andchloro.
 32. An herbicidal composition according to claim 19 in which Yis H.
 33. An herbicidal composition according to claim 19 in which Z isO.
 34. An herbicidal composition according to claim 19 in which m is 1.n is zero. R¹ is trifluoromethyl, R² is chloro, R³ is ethyl, X is H, Yis H, and Z is O.
 35. An herbicidal composition according to claim 19 inwhich m is 1, n is zero, R¹ is trifluoromethyl, R² is chloro. R³ isethyl, X is fluoro, Y is H. and Z is O.
 36. An herbicidal compositionaccording to claim 19 in which m is 1, n is zero. R¹ is trifluoromethyl,R² is chloro, R³ is ethyl, X is H, Y is H, and Z is O.
 37. A method ofcontrolling undesirable vegetation comprising applying to saidvegetation or to the locus thereof an herbicidally effective amount of acompound having the formula ##STR6## in which: R¹ is a member selectedfrom the group consisting of halogen, trifluoromethyl, cyano, CH₃, CF₂CHF₂, OCF₂ CHF₂, OCHF₂, OCF₃, SCH₃, S(O)CH₃, SO₂ CH₃,methoxyiminomethyl, methoxyimino-1-ethyl, benzoyloxyiminomethyl,benzoyloxyimino-1-ethyl, pyridyloxy, and pyridyloxy substituted with oneor more members of the group consisting of halogen andtrifluoromethyl;R² is a member selected from the group consisting ofhalogen, cyano, carboxy, carbalkoxy containing an alkyl group of 1 to 8carbon atoms, and carbalkoxy containing an alkyl group of 1 to 8 carbonatoms substituted with a member selected from the group consisting ofhalogen, trifluoromethyl and phenyl; R³ is a member selected from thegroup consisting of C₁ -C₄ alkyl and C₂ -C₄ alkenyl; X is a memberselected from the group consisting of H and halogen; Y is a memberselected from the group consisting of H and halogen; Z is a memberselected from the group consisting of O and S; and m and n areindependently zero or
 1. 38. A method according to claim 37 in which mis 1 and n is zero.
 39. A method according to claim 37 in which m is 1and n zero and R¹ is a member selected from the group consisting ofhalogen, trifluoromethyl cyano, and pyridyloxy substituted with one ormore members of the group consisting of halogen and trifluoromethyl. 40.A method according to claim 37 in which m is 1 and n is zero, and R¹ isa member selected from the group consisting of chloro, trifluoromethyl,cyano, and pyrid-2-yloxy substituted with one or more members of thegroup consisting of halogen and trifluoromethyl.
 41. A method accordingto claim 37 in which m is 1 and n is zero, R¹ is trifluoromethyl, and Xis a member selected from the group consisting of H and fluoro.
 42. Amethod according to claim 37 in which m is 1 and n is zero, R¹ istrifluoromethyl, and X is a member selected from the group consisting ofH and fluoro.
 43. A method according to claim 37 in which R² is a memberselected from the group consisting of halogen, carboxy, and carbalkoxycontaining an alkyl group of from 1 to 4 carbon atoms.
 44. A methodaccording to claim 37 in which R² is a member selected from the groupconsisting of chloro, carboxy and carbethoxy.
 45. A method according toclaim 37 in which R² is chloro.
 46. A method according to claim 37 inwhich R³ is a member selected from the group consisting of ethyl andvinyl.
 47. A method according to claim 37 in which R³ is C¹ -C⁴ alkyl.48. A method according to claim 37 in which R³ is ethyl.
 49. A methodaccording to claim 37 in which Y is a member selected from the groupconsisting of H and chloro.
 50. A method according to claim 37 in whichY is H.
 51. A method according to claim 37 in which Z is O.
 52. A methodaccording to claim 37 in which m is 1, n is zero, R¹ is trifluoromethyl,R² is chloro, R³ is ethyl, X is H, Y is H, and Z is O.
 53. A methodaccording to claim 37 in which m is 1, n is zero, R¹ is trifluoromethyl,R² is chloro, R³ is ethyl, X is fluoro, Y is H, and Z is O.
 54. A methodaccording to claim 37 in which m is 1, n is zero, R¹ is trifluoromethyl,R² is chloro, R³ is ethyl, X is H, Y is H, and Z is O.